On the Emergence of Ferromagnetism in LaCoO3 Ultrathin Films

Abstract It is well known that the properties of a crystal evolve as it increases in size from a single atomic plane to that of the bulk. Such size‐dependent transitions can stem from many different origins and depend on minute changes to crystal bonding and composition. A model example is that of LaCoO 3 , which is non‐magnetic in the bulk but can display ferromagnetism at the nanoscale. Here, the evolution of structure‐property relationships is studied in the LaCoO 3−δ /SrTiO 3 (001) system as the thickness of LaCoO 3−δ is increased from a single plane to 10 unit cells. In situ synchrotron X‐ray studies are performed during and post‐deposition to probe changes in the interactions between structure, stoichiometry, and magnetic behavior. Structural quantification indicates that the oxygen octahedral rotation pattern evolves with thickness, due to inherent differences in crystal symmetry between the film and substrate. The change in rotation modifies the required energy barrier for the spin state transition via the Co–O bond length and Co–O–Co bond angle, affecting the appearance of ferromagnetism. Our results highlight the contributions of high spin Co 2+ and/or high spin Co 3+ to respective weak and robust ferromagnetism and the evolution of properties with size in ultrathin LaCoO 3−δ heterostructures.